tert-Butanol → Methyl 2-((tert-butoxycarbonyl)amino)-3-nitrobenzoate

HRID 1977388Notes

Reaction equation

HRID 1977388 reaction equation
C([C:4]1[C:13]([N+:14]([O-:16])=[O:15])=[CH:12][CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7])(O)=O.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:24])C=CC=CC=1.C([N:36]([CH2:39]C)CC)C.[C:41]([OH:45])([CH3:44])([CH3:43])[CH3:42]>CN(C=O)C>[C:41]([O:45][C:39]([NH:36][C:4]1[C:13]([N+:14]([O-:16])=[O:15])=[CH:12][CH:11]=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7])=[O:24])([CH3:44])([CH3:43])[CH3:42]

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 43994772-(Methoxycarbonyl)-6-nitrobenzoic acid

Product 1

HCID 9965968Methyl 2-((tert-butoxycarbonyl)amino)-3-nitrobenzoateYield 70%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of methyl 2-carboxy-3-nitrobenzoate (7.23 g) in DMF (50 ml) was added diphenylphosphoryl azide (11.3 g) at room temperature and then triethylamine (6.7 ml) was added dropwise to the stirred reaction mixture. After stirring at room temperature for 3 hours, tert-butanol (54 ml) was added to the stirred reaction mixture. After stirring at room temperature for 30 min., the reaction mixture was gradually warmed, then heated under reflux for 1 hour and evaporated to dryness. The resultant residue was dissolved in ethyl acetate, washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and water, and then dried. After evaporation of the solvent, methanol was added to the resultant residue and the mixture was cooled to give colorless crystals (6.7 g, 70%).

Workup

  1. stirringAfter stirring at room temperature for 30 min.
  2. temperaturethe reaction mixture was gradually warmed
  3. temperatureheated
  4. temperatureunder reflux for 1 hour
  5. customevaporated to dryness
  6. dissolutionThe resultant residue was dissolved in ethyl acetate
  7. washwashed with dilute hydrochloric acid, aqueous sodium bicarbonate, and water
  8. customdried
  9. customAfter evaporation of the solvent, methanol
  10. additionwas added to the resultant residue
  11. temperaturethe mixture was cooled

Sources & evidence

ORD record
ord-edf11602a8e945b6bb467b8eda5876b5
Source dataset
uspto-grants-2001_05
Patent number
US06232334B1

Reaction notes

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